Process of manufacturing silicabase gel catalysts which includes aging



Aug. 9, 1949. K. D. ASHLEY ETAL 2,478,519

PROCESS 0F MANUFACTURING SILICA-BASE GEL CATLYSTS WHICH'INCLUDES AGING 5 Sheets-Sheet 1 Filed Jan. 16, 1945 Kasi NN 5;, Rf Y o/ E mi N E O Wf mJY NB f@ WH fp Aug. 9, 1949. K. D. ASHLEY ErAL rnocsss oF MANUFACTURING smcA -BASE GEL CTALYSTS WHICH INCLUDES AGING 5 Sheets-Sheet 2 Filed Jan. 16, 1945 KNN VQ:

AUS 9 1949- K. D. ASHLEY Erm. 2,478,519

PRocEss oF MANUFACTURING sILIcA-BASE GEL cA'rALYsTs WHICH INCLUDES AGING Filed Jan. 16, 1945 5 Sheets-Sheet 5 so A// BYz/M.. HM

ATTORN EY Aug. 9, 1949o K, D, ASHLEY ETAL 2,478,519

PRocEss 0F MANUFACTURING sILIcA-BASE GEL cATALYsTs wHIcH INCLUDES AGING Filed Jan. 16, 1945 5 Sheets-Sheet 4 pf/7,25. IE5/M0? ATT RNEY Aug. 9, 1949. K. D. ASHLEY ErAL 2,478,519

PROCESS OF MANUFACTURING SILICA-BASE GEL CATALYSTS WHICH INCLUDES AGING Filed Jan. 16, 1945 5 Sheets-Sheet 5 ATTO N EY Patented Aug. s, 194e UNITED STATES PATENT oFElcE- PROCESS F MANUFACTURING SILICA'- BASE GEL CATALYSTS WHICH INCLUDES AGING Kenneth D. Ashley, Noroton, and Alphons 0. Jaeger, Greenwich, Gonn., assigner; to American Cyanamld Company, New York, N. Y., a

corporation of Maine Appunuen January 1s, 1945, serial No. 513,018

'I'his invention relates to the manufacture of adsorbent gels such as are used as drying agents and catalysts and more particularly to the manufacture of gel-type catalysts containing oxides or hydrous oxides of metals lof the third and fourth groups of the periodic system. While the l present invention may also be used for the production of oleilns of higher molecular weight by the dehydrogenation of higher boiling petroleum fractions such as still bottoms.

An important class of gel-type catalysts in wide commercial use for dehydrogenation and cracking reactions are silica catalysts prepared by precipitating hydrated silica from waterglass solutions, Alumina-silica and other promoted silica catalysts are produced by precipitating solutions containing aluminum, zirconium, titanium, cerium, thorium or their mixtures on. a precipitated silica hydrogel. Representative catalysts of the first class are described in United States Patents Nos. 2,285,314 and 2,287,917. It is a principal obiect of the present invention to provide an improved method for the manufacture of catalysts of these classes, which process is especially adapted to the large scale manufacture of gel-type catalysts of high eiliciency. In their broader aspects, however, some of the features of the present inventionare applicable to the manufacture of any gel-type cataall of the alumina may be replaced by other polyvalent metals such as those noted above. The present invention is adapted for the large scale manufacture of catalysts for use in this process, although the principles thereof are not limited to the production of catalysts having a'nne particle size. on the contrary, they may be applied 1n the production vof coarse catalyst grains, pelleted catalysts, spherical catalyst particles, extruded catalyst, and in general without limitation as to the nnal form which the finished catalyst material may take.

In order to produce good yields of high-octane gasoline a satisfactory cracking catalyst should have high initial activity. Moreover, because the normal use of these catalysts involves frequent regeneration by exposure to steam and hot oxyv gen-containing gases to volatilize and vburn out carbonaceous deposits, they must posses a satisfactory degree of catalytic activity after repeated regenerations. The following two tests for catalytic activity have therefore been estabv lished by the petroleum industry:

'then at 16.52 F. for six hours.

1.-Imt1a1 activity 2.-Thermal stability The vapors from the catalyst are` cooled to room temperature and the condensate subjected to an Engler distillation.

They portion boiling below room temperature is called uncondensed gases and that boiling up to 400 F. iscalled gasoline. The total quantity of gasoline and uncondensed gases is compared with the quantities produced with a catalyst which has been adopted as a standard by the industry. The results are expressed as percentages; i. e.,l an initial activity of means that the total amount of gasoline and non-condensable gas is the same as that produced from the same charging stock by the standard catalyst.

The test for initial activity is run on the fresh catalyst as manufactured. The test for thermal activity is run on the fresh catalyst after it has been heated for two hours at 1112 F. and n A minimum specification of 50 (i. e., 50% vof the initial activity of the standard catalyst) have been established for thermal stability or activity.

Objects of the invention The-large size and enormous daily capacity of the fluid catalyst cracking units results in a daily demand for car-load quantities of vcatalysts by the petroleum industry. This is an unprecedented demand in the field of catalysis. In order to supply this demand, `it is apparent that a satisfactory manufacturing process must operate on a large scale, and preferably continuously. Laboratory or small-batch techniques such as those described in the above-mentioned patents cannot be used. In order to obtain the necessary resistance to high temperatures, the alkali metal content of the catalyst must be reduced to a very low figure. preferably less than 0.05%. and this requires the dewatering and washing of many hundreds or even thousands of tons of gelatinous silica slurry each day. Moreover, the high standards of initial activity and thermal stability desired by the industry require an extremely close and uniform control throughout each step of the process.

It is a principal object of the present invention to provide manufacturing methods for the production of catalysts of the class described above, which methods will operate. satisfactorily on a large industrial scale. This object includes the Y.

Y provision of manufacturing processes which will stitute a serious problem in the large scale production of catalysts of uniform `quality.

Outline of the process The general methods for the production of gel-type catalysts containing a siliceous skeleton of high surface activity promoted by a content of alumina or other polyvalent metals include the following principal steps: (a) Precipitation of hydrated silica from alkali metal silicates such as sodium water-glass.

(b) Deposition or coating of alumina and/or ma' polyvalent metal oxides on the hydrous (c) Removal of alkali metal and other impurities from the silica before or after coating.

(d) Dehydration and caleination to form the finished catalyst. Although these four steps are outlined in the above-mentioned patents. it will be noted that the procedures used are those of the laboratory. and do not constitute a' large-scale commercial manufacturing process. The present invention, on the other hand, modifies and supplements the laboratory procedures outlined in Vthese and other similar patents in 'such a manner that the catalyst produced on a tonnage basis by the commercial manufacturing plant will have an initial activity and thermal stability as good Vor better than the laboratory products described in these patents. The invention is based on our discovery that various factors entering into the formation, aging, coating and filtering of hydrated silica slurries and the dehydration and calcining of the resulting catalyst material slurrles have a profound effect on the initial activity and thermal stability of the finished catalyst.

This is true for the following reasons:

The initial activity of a cracking catalyst is dependent largely upon the porosity, capillarity and surface area of the product. A catalyst having a high initial activity a tremendous number of capillaries, and therefore an enormous surface area per gram of catalyst'. Unfortunately, however. excessive porosity with its resulting high adsorptive. properties may have a detrimental effect on the very important property of thermal stability. for the walls of the catalyst may be too thin and weak to withstand the process of regeneration. In lun-ning out the carbon deposits during regeneration the high temperature conditions together with the steam ined and that generated by the combustlonwill tend to break down and thereby reduce the active centers or specific surface of the internal structure of the catalyst granules. and sumcient. rigidity and mechanical strength to withstand this action is necessary to obtain good thermal stability. It is evident, therefore. that an optimum mean value must be established between the highest possible yiriitlitl activity and the highest thermal stability,

and this is the reason for the standard test values of 90-100 for initial activity and 50 or better for thermal stability that have been established thepetroleumindustry.'

Precipitation of Maratea una :lumen The methods which'we employ for the precipitation and fiocculation of hydrated silica slurries of the type which will produce catalysts of optimumproperties are describedlgenerally in our copending application Serial No. 459,262. f iled September 22, 1942, now U. B. 2,411,820, of

A solution of sodium or potassium silicate is prepared in a mixing tank provided with suitable high speed agitators. preferably at a concentrae tion which will form a slurry containing about 34% of 810sA in the form of gelatinous silica after acidification. sulfuric, hydrochloric. nitric or othes mineral acid is added over aperiod not less than 15 minutes, and preferably 30-40 minutes.y

in the amounts necessary to precipitate the silica. The acidification is preferably carried out by adding 25% sulfuric acid in a continuous well-distributed stream.l to a ilnal pH of about 4-8.

' After a complete acidification in this matter 16% aqua ammonia solution is preferably added to raise the pH to about 8.7, which is the optimum value for aging.

The factors involved in 'the process (temperature, concentration of solids, pH and aging time) are very closely interrelated, and must be considered together. Because of the large quantities of water used it may not be feasible to'maintain a close control of the temperature of the process water or of the waterglass solutions; however, we have lfoundv that the otherV factors may be varied to compensate for seasonal temperature differences. We have found that in summer weather the vconcentration of the silica solution should be such as to form a silica slurry having a solids content of about 3.545%, whereas in winter weather the solids content may be raised to 4.51596 with an optimum value of 5%. However, unusually low solids contents may result in excessively/,high densities in the finished catalysts, as is shown in Fig. 5 of the drawings, and should be avoided.

The particle size of the grains of gelatinous silica should be carefully controlled to promote alkali metal removal. A catalyst of good activity can be obtained from slurries having a very ilne particle size. but such slurries are extremely difwater-soluble salts are not completely removed from the grains of silica. We find that a slurry wherein more than 95% of the particles will pass through a thirty-mesh sieve but will be retained by a 30G-mesh sieve should be employed. This particle size may be obtained by means of a turbine type agitator provided with a well-distriba uted acid supply and surrounded by a screen having 6 to 8 meshes per inch which produces lines of shear in the solution during the acid addition. A precipitator or strike tank equipped with suitable agitators is shown in Fis. 8 of the drawings.

Aging the hydrated silica In our @pending application serial No. 459,262.

now Patent No. 2,411,820, dated November 28,

" 1946, we discussed the importance of a preliminary nocculation of the hydrated silica slurries.

In that application we stated:

v and calcined. The most important feature of our pretreatment is referred to hereinafter as a nocculation step and the silica so treated is referred to as iiocculated silica, but it should be understood that these terms refer to the condition and behavior of the silica or other hydrated metal oxide during the dewatering and washing thereof rather than to any noticeable change in the aqueous suspensions after the iiocculating agent has been added. In practicing our invention we subject the aqueous suspensions containing gelatinous hydrated silica to a conditioning procedure which does not materially change the density, appearance or degree of dispersion of the hydrated silica particles in the aqueous slurry, but which so modifies these particles that they form a relatively thick, porous filter cake of good mechanical strength instead of the ordinary thin, slushy filter cakes that are obtained whenordinary gelatinous silica suspemions are filtered. We have found that aging appears to aid materially in obtaining a relatively thick and porous filter cake; in fact, we have noted improvements cluding filtration, settling and decantation, thickening and the like.

. Figures 3 and 5 of the drawings show quantitatively theeect of agingon the activity of the catalyst, particularly with respect to the thermal stability. Aging also is an important factor in obtaining a catalyst substantially free from alkali metal compounds as is pointed out in the above quotation from our earlier application. The factors involved in the aging procedure are (i) time of aging. (2) seing temperature, (3)' pH control and (4) amount of gelatinous silica in the slurry.

Although our invention is not limited by any theory of operation. but is intended to provide a practical manufacturing process regardless of the exact nature ofthe chemical or physical changes involved. we believe that at least three important changes take place in the gelatinous silica during aging. These changes are (a) coagulation or agglomeration of the silica particles to produce a slurry containing grains of favorable and more uniform particle size range with a reduction in the amount of slimes, (b) formation of silicio acid polymers of high molecular weight with concomitant building of the siliceous skeleton of silicio acid gels and (c) progressive dehydration or loss of water of hydration from the silica with consequent thickening and stinening of the walls of the silica gel. The combined effect of these and other results of aging are properly summarized as iiocculation since their` result is to increase the homogeniety of the gelatinous silica, thereby permitting its filtration and washing on a rotary vacuum lter, and to improve the mechanical strength of the gel structure.

- Suitable flocculation is obtained lby operating in in the filtration and washing of slurries of gelatinous hydratedsilica which had been aged for 1-2 hours, but to which no iiocculating agent was added. Our invention in its broader aspects therefore includes the combined steps of aging followed by filtration as one of its important features.

A number of important advantages are obtained by preconditioning pulps or slurries of gelatinous hydrated silica in the manner described above, prior to the dewatering thereof. We have found that inorganic salts such as sodium sulfate, sodium nitrate, sodium chloride and the like can be more rapidly and completely removed from a fiocculated silica slurry by washing as well as by filtration, and the silica can therefore be dewatered by any suitable procedure. Moreover, flocculation of the hydrated silica also results in a final dried product of much greater uniformity in particle size, as compared with the irregular size of the particles obtained by drytained by the ordinary methods heretofore employed. Our invention in its broader aspects therefore includes the dewatering and washing 'of iiocculated silica by any suitable method ining hydrogels of silica or silica and alumina obaccordance with the following principles:

Under constant conditions of temperature and solids content there is a decided improvement in the filtration characteristics of the silicaslurries with increased aging up to a certain optimum value, after which further aging produces little or no improvement. The aging time necessary to reach this optimum filtration value, which is also the optimum for producing a catalyst of enhanced thermal stability, decreases with a moderate increase in temperature of precipitation and aging of the slurry, up to a value inthe neighborhood of 100 F. At higher temperatures there is a marked deterioration in filtering characteristics and catalytic activity regardless of the degree of aging. The aging time is also shortened -by an increase in the silica content of the slurry up to about 6%, Aging at higher solids content than 6% is not commercially feasible because of the liability of continuous gel formation. These tors are illustrated in Figs. 3-5 of the draw- Aging of freshly precipitated silica slurries, obtained by the addition of an acid such as sulfuric acid to alkali metal silicate solutions, should be carried out within a pH range between about 5.15 and 8.1. Aging at acidities below a pH of about 5.5 does not result in fiocculation of the silica. Within the range specified, there is very little change with changes of the pH value; however, a ypH of around 6.5-7 appears to `be optimum for 'best filtering and washing of the catalyst gel. After the aging is completed, however, the pH should be reduced to about 44.8 to

oiltain complete removal of alkali metal from the s ca.

The gel structure, apparent density'and thickness and physical strength of the walls-of the n solids during the precipitation and aging of the gelatinous silica, and therefore `these factors should be closely controlled to obtain optimum thermal stability consistent with high initial activity in the catalyst. Ther-mal stability in the catalyst increases with increased aging time. since the aging tends to strengthen and thicken the walls of the silica skeleton; however, this same thickening necessarily results in some loss of initial activity in the catalyst. We have found, however. as one of the principal features of our invention, that when the precipitation and aging are controlled in the manner described above there is obtained a catalyst having optimum thermal activity and a long effective life as well as very satisfactory initial activity.

Precipitation of alumina The aged gelatinous silica is impregnated or coated with alumina, or with a mixture of alumina and zirconia or other ingredients capable of functioning as activating agents. The coating step may be carried out either before or after the silica has been dewatered and washed to remove soluble salts and residual combined alkali metal. Both methods of coating are illustrated in the attached drawings. and both are included within the scope of the invention.

The coating is preferably carried out by adding the proper quantity of coatingmaterial in the form of a water solution of sulfates, nitrates or other water-soluble salts of the coating metal or metals. agitating to obtain a uniform mixing, and then precipitating by the addition of an which is preferably ammonium hydroxide. vBefore adding the coating solution, however, it. is important to add sufcient 25% sulfuric or other acid corresponding to the anion of the coating salt to reduce the pH of the silica slurry to an extent which will prevent a preliminary and uncontrolled precipitation of coating material in the silica before uniform mixing is completed. When aluminum sulfate, is used as the coating material the pH should be reduced to about 34.5; other coating salts may require a dierent pH that a pH oi' 45.5` is optimum and results in a filter cake of about 0.75 inch thick which is easily washed.

When the silica slurry has been properly processed and its physical condition is righ-t the hlterlng operation is continuous and snooth. The speed of the filter can be varied over a fairly wide range, peripheral speeds of from 3 to l feet per minute being about the optimum range.

but better results are obtained with lower speeds within this range.

The wash water should be applied continuously to the filter cloth at all times during the ultervalue. We have found that the filtering characterlstics of the impregnated slurry are much improved by this preliminary acidification.

The coating solution is preferably added during a period of about ten minutes and agitation is continued for an additional ten minutes to obtain complete mixing. A 16% aqua solution is then introduced over a period of about 25-30 minutes with constant agitation. When the pH rises to 5-5.5 the ammonia addition is stopped and the slurry is ready for dewatering.

4 Filtrationand washing By proper control of the process variables discussed above, we have succeeded in improving the filtering characteristics-of both coated and uncoated silica slurries to such an extent that the dewatering can -be carried out continuously on a rotary vacuum-filter, and this is one of the principal advantages of our invention. The nltration characteristics are profoundly affected by the pH of the coated or uncoated silica slurry just prior to the nrst filtration step. Too low a pH, such as one substantially -below 4.0, produces a thin and sli-my illter cake which blinds the filter cloth and quickly reduces the capacity of the nlter. A high pH results in a cake which is too thick for emcient washing. We have found ing operation. It is preferably applied by atomizing low pressure sprays applied uniformly over the exposed surfaces of the filters, starting immediately after the cake leaves the bath and stopping at the point of cake removal. If not enough water is used at any one point, and the cake is sucked dry for even a very short time, the cake immediately cracks and the efiicieucy of washing is greatly reduced. If too muchwater is used, inadequate washingresuits because the cake is relatively soft and slimy, particularly on the first filter. About 3-4 gallons per minute ef wesh water eemmed te e -pn of 3 5 is applied' to each square foot of exposed hlter area on all filters except the last with preferably a. pH of about 3 on the second and third. 0n the last lter the pH of the wash water is preferably 4.2 and the quantity is reduced to about half.

Denyaratien and :eazematm The coated catalyst gel leaves the last filter with a moisture content of about and must be dehydrated and calcined to produce the iinished catalyst material. This means that about ten tous of' water must be evaporated for each.

. while the last stage completes the removal of uncombined moisture and also removes the water of combination.'

The dehydration and calcination may advantageously be carried out in brick-lined rotary kilns wherein the catalyst gel passes in countercur-V rent contact with hot. gases from the combustion of coal, natural gas or other suitable fuel. These kilns are preferably set on a slight incline and are provided with retention dams to prevent the catalyst material from flooding through the kiln. While there is little danger of overheating in the -irst dehydration kiln, care should be taken to avoid direct contact of flame with the Acatalyst material at any time, and the catalyst should not ge heated to temperatures higher than BDO-1200' Considerable quantities of ilnely divided catalyst are frequently blown from the kilns by' the gases. and therefore it is advisable to pass these gases through a spray tower for its removal and recovery. Experience has shown that the catalyst recovered from the gases in this manner is Y comparable in quality and activity with that obtained from the catalyst discharge ofl the kiln, and therefore the recovered catalyst dust can be mixed with the plant product.

A very important and unexpected advantage resulting from operating in a rotary kiln in countercurrent contact with hot gases is the fact that a large proportion of the residual sodium, po-

l tassium or other-water-soluble salt is removed from the catalyst gel during the caicination. This is an important feature of our invention, for it' permits us to feed to the dehydrators, if desired, a wet filter cake having a content of sodium sulfate or other water-soluble impurity considerably of the nlters.

Apparently the removal of water-soluble salts results from the volatilizing action of the hot gases in the kiln. In the dehydration of the capillaries, minute crevices, 'pores and tiny passages, the steun formed by heating the catalyst is apparently evolved at fairly high velocity and carries with it the water-soluble salts that were dissolved in the water evaporated. Production records of kiln operation over a substantial period of time have shown that the average removal of sodium as sodium sulfate in this manner is about 80-85% so that a filter cake from the fourth filter conbeen pointed out. For temperatures of 85 F. and higher. 5% solids are practical. whereas below this point 4.5% solids are probably maximum and 4% or lower may be used in winter` weather if the process water is not preheated. Commercial silicate of soda containing about 29% B101 and 834.0% NazO has been used with success. The water used is ordinary water that has been v passed through an ion exchange softening process to remove all hardness and practically all of the -potassium and sodium. Distilled water need not taining, for example, 0.2% NazO will produce a calcined catalyst containing only 0.033% of NazO. When the filtration capacity is such as to produce a lter cake of considerably lower sodium content, such as 0.02% of NazO the percentage removal of sodium during calcination is not materially reduced; therefore in this case the finished-catalyst will contain only about 0.000492,

-of NaaO. These results were obtained in a rotary kiln operating at an average gas inlet temperature of 1200-1400 F. and with a lter cake averaging 10% solids.

When gas inlet temperatures of 12001500 F. are used in the drying kiln and also in the calcining kiln the drying and calcining operations are finished in about 30- 60 minutes. These times are much shorter than those that must be used when other methods of dryingfand calcining are employed.

The principles of our invention will be further described and illustrated by reference to the accompanying drawings, wherein:

Fig. 1 is a flow sheet illustrating diagrammatically a process of catalyst manufacture in which the 'activating coating material is added prior to the rst ltration.

Fig. 2 is a flow sheet illustrating a process in which the coating step follows the first filtration. This figure is substantally the same as the drawing of our copending application Serial No. 459,262 referred to above. l

Fig. 3 is a graph showing the effect of temperature. solids content and time of aging of uncoated silica slurries on the initial and thermal activities of the catalyst.

Fig. 4 is a graph showing in greater detail the effect on thermal activity of the silica content of the slurry.

Fig. 5 is a graph showing the effect of agin time and temperature on the apparent density of the finished catalyst.

Fig. 6 is a vertical section, with parts shown in elevation, oi' a suitable precipitator or strike tank for precipitating the gelatinous silica.

Referring to the process of Fig. 1, it will be seen that a dilute aqueous solution A of sodium silicate is first prepared in the precipitator or strike tank i. preferably at a concentration which will form a slurry containing Iabout 3-6% of gelatinous silica after acidification. The exact concentration may be varied with the temperature of the process water, for reasons which have.

'Ihe arrangement of the agitators and degree of agitation in the strike tank i is important. and therefore this tank is shown in detail in Fig. 6 of theA drawings. Referring to this gure it will be seen that the tank i is an open cylindrical tank, preferably of wooden construction, containing a large gate-type agitator 2 made up of a number of vertical staves 3 attached to crosspieces 4 which in turn are suspended from a central drive shaft 5. The tank is also equipped with a high speed turbine-type agitator 6 having curved blades 1 attached to a shaft 8 which passes through the bottom of the tank through a stuiilng box S'and is driven by gears. I0 at a speed of approximately 80 R. P. M. This agitator is mounted on the floor of the tank, as by a base plate I I and bolts l2 and is fitted with an annular framework i3 having an outer cylindrical screen il laterally of the blades 1. In operation the silica slurry is drawn in at the top of the |agitator, as indicated by the curved arrows, and is discharged through the screen, which serves to break up lumps or pellets of gelatinous silica and produce a slurry of uniform particle size. The

is pumped to the aging tank 20. The object of overacidifying the batch is to insure complete thermal activity of the catalyst.

The aging in tank 20 is carried out under relatively gentle agitation by means of a gate-type agitator 2l. The importance of this step has been discussed. After suitable aging the batch is coated, and this may be done either in the tank where the aging was carried out, or in the separate tank 22 that is illustrated in the drawing.

In the preparation of a catalyst consisting of silica and 10% alumina, an aluminum sulphate solution containing the equivalent of '1% A: is preferably employed. This alum solution is preferably introduced through a perforated trough at the top of tank 22 to obtain uniform mixing without local overconcentration. After complete mixing a 16% ammonia "solution is introduced into the tank, preferably through a submerged perforated pipe, in amounts sufilcient to raise the pH to 4.5-4.8 as shown by the pH indicator 23. The batch is then passed to the feed tank 2|, andfrom there it is pumped to the first stage filter 25.

The details of the filtration have been discussed above, and need not be repeated. However, it

may be stated that the wash waterA on each of amano 1 l the nlters is processed water containing substantially no hardness or alkali metal ions. acidiiied with sulfuric acid. The filters 2i, 2t and 21 are l l2 cekeonaconveyorbeltleadingtothedryinl kiln. The tour filters show the following typical performances:

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Asnotedabove.eachoftheflrstthreeiiltera Oliver-type rotary drum iilters. the second and third having feed tanks 28 and!! which receive repulped slurry from the preceding iiltration stage. Each nlter is provided with a wash water trough on the pick-up side of the wheel which collects surface wash water that would ordinarily run into the vat lo and delivers it through lines 3l, I2 and 33 to the feed tanks Il. 2! and Il respectively. This prevents dilution of the slurry in the vats feeding the filter cloths. and assiste greatly in maintaining the slurry at the proper solids content for nltration.

The following is a speciilc example oi' operation in accordance with this embodiment of our invention:

253 gallons of il B. silicate of soda are diluted with 1580 gallons Vof puriiled water in the tank l and acidiiied with approximately 170 gallons oi 25% sulfuric acid by the procedure described above. The volume of ammonia for raising the pH to 6.7-6.8 is negligible. The batch is then pumped by air displacement pump-S to the inl tank and tank I is rinsed with about 100 Sallons of watcr which is added to the batch in tank 20. This results in a slurry containing 4.5% of S102.

Although only one aging tank is illustrated in the drawing, it should be understood that a number of these are used in actual practice; the ex- "nxation of sodium in the nlter cake. presumably by forming a zeolite. agitation during the aging is important; it should be gentle so as not to break up the gel structure. but sumcient to facilitate the leaching of the sodium sulfate into the solution proper. The agitator 2l is therefore operated at about 'i6-20 R.. P. M. An 881118 time of two hours is standard practice with a slurry temperature of about 80 Il.; with slurries of lower temperature the aging time may be lengthenedtoasmuchasnvehours,asisindicatedon Fil. 3 of the drawings.

After aging. the batch is introduced into the coating tank 22, where sulfuric acid is added in amounts such as to reduce the pH to about 3.5. Then 127 gallons of 7% A120: equivalent aluminum sulfate solution is run in over a period of lo-minutes, and agitation is continuedj for an additional 10 minutes. This brings the pH down (to 33.2. About 6l gallons of 16% aqua ammonia is next introduced, sudlcient being used to raise thepH to 5.2-5.3. This precipitates the alumina. naidartshebatchisuowreadytobepumpedtothe Each oi' the three filters il, It and 21 discharges into a repulper supplied with overflow water from the next succeeding Viilter vat. as indicated on the drawing. The fourth and iinal is continuously wet with suiilcicnt wash vgive a double displacement wash.

The consumption of wash water is about 500 per minute in a plant producing 25-30 catalyst per 24-hour day.

Thcnltercakefromthefourthiilteris to about Sir-65% moisture in the iii-st of rotary kilns by countercurrent contact with products of combustion. which enter the kiln l200l500 l'. and leave at 40o-45o P. product is then calcincd in the second kiln tionofsodiumorpotassiumsilicateinamixing tank 4i, which is provided with suitable agitators 42 to obtain uniform mixing of the charge. The diluted waterglass solution is neutralized with sulfuric. hydrochloric. nitric or other mineral acid to a pH of about 7.4-7.8, after which the agitation is continued for about 55 hour. The amountsandstrengthofthereagentsaresuch that the solution contains about 5% SiO.

After the preliminary acidification the contents of tank li are discharged intotank whichisacorrectiontankequippedwitha suitable agitator and of a size sumcicnt to permit a retention of the charge for about 'i5 minutes. At thispointitmaybestatedthatemceptwhere otherwisenotedallthetankssubsequenttotank 4l are equipped with agitators which move very siowly.sothatthereisnotendencytobreakup orredispersegelsthathavesettledorbeenilocculated. In the tank I3 sumcient additional acid is added to bring the pH to about 'M2-7.8 and sumcient additional water to reduce the BiO: content to 3.8%.

Alter suitable retention in the correction tank I3 the gelatinous hydrated silica slurry resulting iromtheacidadditionanddilutionispassedto a blending and aging tank Il, wherein it may be aged under slow agitation for any suitable time. Agingoftheslurryappearstoincreasetheaverage particle size of the silicaA either by agglomeratlon of thc' smaller partheles or by their adhesion to larger sized particles. The aged slurry may then be delivered directly to the first filter u without additional floeculation. or it may v bepassedtothetankiortheadditionofa nocculating agent to furtherl improve its nitration and washingcharacteristics. Inthistank theslurryisfirstbroughttoapHofQ-d'bythe v addition of suitable amounts of sulfuric acid nlter, which is not shown, discharges its nlter othermineralacidaft'erwhichanadhesivecollold?? is added. Repruentative adhesive colloids that we have used with success for this purpose are glue. gelatin. gluten and gluten-containing matev rials such as wheat flour and the like. These and similar fiocculating agents are preferably employed in amounts of 0.001% tc-0.1%, based on the weight of the slurry. and are distributed uniiormly through the hydrated silica slurry by slow agitation.

The aged and fiocculated suspension is pumped to a distributor box 4I. which is a wooden vbox of relatively large cross-sectional area provided with one or more vertical partitions 41 and adapted to maintain the silica in a fiocculated condition 48. This may be an ordinaryiilter press or any other known type of filter, but is preferably av rotary filter of the vacuum drum ltype provided with fine water sprays for continuous washing of the filter cake. in order to aid in the separation of salts of alkali metals and other undesirable materials from the silica.

On the filter 48 the silica can be washed free from the major part of its water-soluble impurities by wash water which may be acidied with a little sulfuric or hydrochloric acid, the filtration and washing being greatly aided by the fiocculation of the silica. In large scale operation the`wash water from this and other similar washing steps of the process is preferably regenerated for reuse by contact with a cation-exchange resin such as sulfonated coal, which removes the sodium ions and regenerates free sulfuric acid or hydrochloric acid in the solution. The washed filter cake is then discharged into a repulper 48, which is an enamel-lined vessel tted with a horizontal agitator 50 which may be a relatively high speed agitator. In the repulper the filter cake is again dispersed in water to form a uniform slurry for further treatment.

In the preparation of catalysts or catalyst carriers consisting essentially of silica the slurry from the repulper 49 may be passed through line 5i to a fiocculating and adjusting tank 52 wherein the silica may be aged and flocculated by the addition of a flocculating agent if desired. In preparing mixed catalysts containing the active silica together with other catalytically active metal oxides and/or hydrogels the silica slurry is first passed to one of the two tanks 53 and 54. A

solution of aluminum sulfate or other salt of the desired metal is then added to the slurry suspension after which sufficient ammonia is added as ammonium hydroxide to precipitate the hydrated metal oxide from its salts. Thus, for example, in the preparation of a silica-alumina catalyst of the type described in U. S. Patent No. 2,285,314 a solution of aluminum sulfate in water is added to the slurry of silica in the tank 53 under continuous agitation during one-half hour after which 8% of aqua ammonia is added during 10-20 minutes to bring the pH to 4.5-5.7. In the preparation of modified catalysts a small amount of zirconium or titanium sulfate may also be added and precipitated. By employing the tanks 53 and 54 in parallel it is possible to handle a second batch of the semi-purified silica while the alumina or other polyvalent metal is being added to and precipitated in the first batch, and any number of tanks may be employed in this manner in large scale operation.

After the addition and precipitation of alumina or other metal salts in the tanks 53 or 54 the re- `sulting slurry is introduced intothe aging and suitable fiocculating agent may be added in ap.

proximately the same quantities' that were used inthetank45ifdesired.butthisisnotusually necessary since the hydrated aluminum oxide makes the slurry much easier to filter. In the tank Il the slurry is preferably adjusted to 4.5-696 solids by the addition of water if necessary, and kept under slow agitation until the hydrated alumina-silica mixture is ready for filtration and washing. It is then passed to the filter I. which is a rotary filter similar to the filter 48. and the fiocculated solids are separated from the accompanying salt solution and washed with acidified water as before.

In order to reduce still further the content of alkali metal salts. ammonium salts, and other undesirable water-soluble 'material from the silica-alumina mixturathe filter cake is again preferably reslurried in water in a second repulper 5l and again filtered on a rotary filter 58, with or without reiiocculation and aging in tank 58 depending on the condition of the solids at this point. The filter cake from the filter Il may .then be reslurried once more in the repulper 60 if desired. brought to a solids content of 5% and a pH of 4.3-5.0in the tank 5I and filtered on the rotary filter 52 which is washed with water to remove the remaining water-soluble impurities. The lter cake is then removed at approximately solids onto a belt conveyor 53,

which discharges it into a calciner 64.

Because of the large quantities of water retained by gelatinous hydrated silica or silicaalumina mixtures a relatively large drier or calciner is necessary. In` some cases, however, we have found that the purified gelatinous filter cake can'be advantageously dried and calcined by a plurality of drying stages. Thus, for example, we may subject the wet filter cake to hot air or other drying gases by supporting it on a belt or other conveying mechanism which is passed continuously or intermittently through a drier of any suitable type, such as a hot air or steam heated drier. By this means we may remove as much as to 60% of the water in the filter cake, after whichthe drying of the partially dried gel may be completed in a calciner of the rotary kiln type. Alternatively, the drying may be carried out in one or more rotary kilns. and such a calciner is illustrated on the drawings.

The calciner is preferably direct-fired in a fire box and sufiicient capacity is provided to heat the catalyst to temperatures of G-700 F. before it is discharged. The driedmaterial is then ground in a grinder 66 to 40-mesh size and is obtained as a product containing not more than 0.05% NazO and little or no FezO: or other undesirable materials.

In practicing this embodiment of our invention, 4.36 tons of sodium silicate in the form of commercial waterglass was added to the mixing tank 4| together with 18.4 tons of waterI and after completing the dilution 2.2 tons of 24.9% sulfuric acid were added. After agitating for one-half hour the resulting slurry was passed through the correction and aging tanks 45 and 44, as previously described, and 0.015% of glue was added in the fiocculating tank 45. After suitable fiocculation the solids were then filtered off on the filter 48 and washed with 30.9 tons of water containing suflicient sulfuric acid to reduce the pH of the Xwash water to 2.8. The washed filter cake was repulped with 9.6 tons of water in the repulper 48 and run into tank auatic Y It. where a solution of 0.8 ton of aluminum sulfate in 1.6 tons of water was added. '111e alum was then precipitated by the addition of 1.87 tons of 8% NHiOH solution and the resulting slurry was iiocculated in the tank ll by the addition of 0.015% of glue as before. After the following nltraticn step the cake on the filter Il was washed with 25.5 tons of water containing sufficient sulfuric acid to reduce its pH to 2 5-3 and repulped in 12.9 tous of water. iha same quantities of dilute acid and water were used on the iilter Il and repulper Il. but 21.9 tonsoipurewaterwereusedtowashtheillter cake on the tllter l2. .After the calcination 1.20 tom of an oil-cracking catalyst were obtained which contained 90%.8103 and 10% A130: in a highly active condition.

The following is an example of thepreparation of a pure silicacatalyst by applying the principles of our invention:

12.5 lbs. of 41 B. sodium silicate containing 8.5% of NaaO and 28.5% of S10: was diluted with 52.5 lbs. of pure water in a mixer of the turbine type (see Chemical Engineering Hand` book. p. 1288). 6.5 lbs. of 25% sulfuric acid were added with vigorous agitation during -30 minutes. after which the mixer was emptiedl and washed with 24 ibs. of water containing 0.3-0.4 lh. of 25%. sulfuric acid. 'I'he wash water was `added to the precipitated silica slurry and the mixture was aged for 1.5-2 hours at a pH of 7.0-7.3. A water solution of glue was then added in amounts of U01-0.02% of glue and the iiocculated hydrous silica-was dewatered by illtration. A dried sample of the filter cake contained 0.22% sodium.`

The filter cakerwas washed on the illter with an amount of wash water' equal to the original weight of the slurry. sludged up with a little water and aged for 12 hours. It was then dilut- 40 ed with water to 4-0% solids. 5% being the preferred figure, 0.015% of glue was again added, andthesilica slurry was againilltered andthe filter cake washed with acidiied water. The sodiumV content of a dried sample of the lter cake was 0.02%. The aging. occulation, filtration andwashingwasrepeatedathirdtime. butin thiscasenoacidwasusedinthewashwater. 'nais reduced the sodium content to 0.01%. The

iter cake was then dehydrated and calcined as previously described and the resulting pure silica catalyst was ground to 4-8 mesh. It was Awell suited for use as a dehydration catalyst for the production of butadiene from butylene glycols.

In the foregoing specification we have described in detail the principles and most important features of our invention, which are il- 05-75 F. while a second batch is being aged at.

00-90 1l'. The two batches may then be mixed together. Similar variations may be made in the p11 of two or more batches, one being aged at a pl-I of 5.8, for example, the second at a pH of 0.5 and a third to a pH of 7.0, after. which the three batches may be mixed. Other variations of this nature will be apparent from the foregoing description.v

One important method oi' applying the principles outlined above is of particular commercial importance in avoiding the seeding effect of overaged material.` In the daily operation of a catav lyst manufacturing plant by the procedure outlined on Fig. 1 ofthe drawings it sometimes hapu pens that one or more of the batches maybecome dehydrated to too great an extentby overaging. In order to avoid the effects of this condition, an occasional batch may be mixed with preceding or subsequent batches in an unaged condition or after an only partial aging. Greater imiformlty -in the quality of the plant product is obtained by this procedure. 1

What we claim is:

1. A process for the manufacture of adsorbent silica gels of high porosity and adsorptive capacity but resistant to loss of activity on heating which comprises precipitating hydrated silica in granular condition from an aqueous alkali metal silicate solution by agitating and acidifying the solution. flocculating the hydrated silica in the resulting slurry by aging with' agitation at a pH of 5.5-8.1 for 0.5 to 5 hours at a temperature within the range of 40100 F.. and at a solids content of 3.5-6%, repeatedly filtering while maintaining the aged slurry at a pH of about 4-5.5 and washing the filtered solids to remove dissolved salts, and drying and calciumg the filtered solids by passing them through a rotating kiln in countercurrent contact with hotgases entering at a temperature of 1200-1500" F.

2.l A proces for the manufacture of an activatcd silica gel catalyst of high porosity and adsorptive capacity but resistant to loss of activity on heating which comprises precipitating hydrated silica in granular condition from an aquelowing are illustrative of the flexibility in operation that can be obtained by applying the principles of our invention:

The controlled aging of the silica slurry enables us to obtain many important advantages in catataueous improvement in both characteristics by varying the conditions of silica precipitation and aging from batch to batch. Thus. for example.

ous alkali metal silicate solution having a concentration such `as to produce a precipitated slurry of 3.5-6% solids content by acidifying the solution with strong agitation, ilocculating the.

3. A method according to claim 2 in which the hydrated silica is precipitated by acidifying the alkali metal silicate solution while forcing the slurry through a screen having openings of 6-8 per linear inch.

4. A method according to claim 2 in which the l 7 slurry i-s filtered and washed on a 'continuous rotary filter at a pH of 4-5.5.

5. A method according to claim 2 in which the filtered solids are calcined by countercurrent contact with hot gases having an entering temperature of 1200-1500 F.

6. A process for the manufacture of an activated silica gel catalyst of high porosity and adsorptive capacity but resistant to loss'of activity on heating which comprises precipitating granular silica from an aqueous alkali metal silicate solution by acidifying the solution with agitation to a pH of 4-6, then fiocculating the slurry by aging at a pH of 5.5-8.1 and at a. temperature within the range of 40-100 F. for 0.5-5 hours with gentle agitation at a solids content of 3.5- 6%, then precipitating aluminum oxide on the silica and repeatedly ltering the resulting slurry and Washing to remove water-soluble salts at a pH of 4 to 5.5, and finally calcinating the filtered catalyst-forming material bypassing it in countercurrent contact with a stream of hot gases.

7. In a process for the manufacture of an adsorbent silica gel having a low content of watersoluble salts, the method of obtaining a iilterable precipitate of grains of hydrated silica of relatively uniform particle size which comprises forming a two-phase slurry consisting of small grains of hydrated silica suspended in a continuous aqueous phase by adding to an aqueous alkali metal silicate solution a sulicient quantity of an acid to acidify the mixture, the concentration of the acid and of the alkali metal silicate solution being such that the resulting slurry contains about 3% to 6% of S102 after acidification, and continuously recirculating the slurry during its formation through a screen of approximately 6 to 8 meshes per inch to produce lines'of shear therein.

8. A method according to claim 7 in which the resulting slurry is iiocculated by aging with gentle agitation at 50-100 F. for 0.5-5 hours at a pH agitation, then occulating the slurry Iby aging it for 0.5 to hours at a pH of 5.5-8.1 and a solids content of 3.5-6% at temperatures of 50- 100 F. with gentle agitation, then precipitating aluminum oxide on the silica, repeatedly filtering the resulting slurry and washing to remove l water-soluble salts and finally drying and calcining the filtered catalyst-forming material to .form a hard, porous gel.

10. In a process for the manufacture of an adsorbent silica gel having a low content of water-soluble salts, the steps which comprise aging an aqueous hydrated granular silica slurry having a solids content of 3.5-6% and a pH of 5.5-8.1 at temperatures of 50-100 F. for 1-5 hours and filtering the silica after aging on a continuous rotary iilter at a pH of 4-5.5 while continuously wetting the entire lter cake with wash water.

11. A process for the manufacture of a silicaalumina gel catalyst of high porosity and adsorptive capacity for the catalytic cracking of petroleum hydrocarbons by the iiuid stream" 18 process which comprises precipitating hydrated silica in granular condition from an aqueous alkali metal silicate solution by acidifying the solution with strong agitation, vflocculating the resulting hydrated silica slurry by aging at a solids content of 3.5-6% and a pH of 5.5-8.1 and at a temperature within the range of 40- 100 F. for 0.5-5 hours, precipitating aluminum oxide in the silica slurry, repeatedly filtering the resulting silica-alumina slurry and washing to remove water-soluble salts, calcining the filtered catalyst-forming material by passing it through a rotating kiln in countercurrent contact with hot gases passing through the kiln at a velocity such that substantial quantities of catalyst are blown from the kiln by the gases, separating entrained catalyst from the exit gases from the kiln and mixing the catalyst so separated with the main body of catalyst product.

12. A method of producing an activated silica gel catalyst having an alkali metal content less than 0.05% MezO which comprises preparing a catalyst-forming composition composed of grains of hydrated silica containing a smaller quantity of alumina, about of wate'r, and a content of water-soluble alkali metal salts greater than that corresponding to 0.05% MezO but not greater than 0.1% on a dry basis and drying and dehydrating said composition by passing it in countercurrent contact with hot gases having a temperature of 1200-1500 F., whereby a major proportion of the water-soluble alkali metal salts is removed from the composition along with the Water and the alkali metal salt content of the dry-catalyst is reduced below that corresponding to 0.05% MezO.

13. A method of preparing a silica-containing catalyst which comprises the steps of forming an aqueous slurry of gelatinous silica containing water-soluble inorganic salts, adjusting the pH of the slurry to 5.5-8.1, aging the slurry for 0.5-5 hours at 40-100 F. at a solids contentof 3 5-6%, adjusting the pH of the slurry to about 3-3.5, adding an aqueous aluminum sulfate solution to the slurry and precipitating alumina therein by raising the pH to 5.0-5.5, and separating the alkali metal salts by dewatering and washing the slurry. A

f KENNETH D. ASHLEY.

ALPHONS O. JAEGER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Date Number Name 1,577,186 Patrick Apr. 6, 192g 1,579,262 Vickery et al. Apr. 6, 192A, 1,665,264 Holmes Apr. 10, 1928 1,832,153 Stoewener Nov, 17, 1931 1,900,859 Connolly et al. Mar. 7, 1933 1,958,710 Moyer May 15, 1934 2,270,090 Thomas Jan. 13, 1942 2,280,650 Kassel Apr. 21, 1942 2,323,583 Wilson July 6, 1943 2,326,523 Connolly et al. Aug. 10, 1943 2,326,706 Thomas et al. "Aug. 10, 1943 2,331,473 Hyman Oct. 12, 1943 2,412,958 Bates et al. Dec. 24, 1946 OTHER REFERENCES 

